Carbamoyl sulfoxide derivatives

ABSTRACT

Intermediate compounds useful for manufacturing herbicidal active sulfoxide compounds are described herein. The compounds have the following generic formula:   wherein R is selected from pyridylalkyl, R1 and R2 can be the same or different and can be selected from the group consisting of lower alkyl, cycloalkyl, alkenyl and benzyl.

Unlted States Patent 1 m1 3,910,935

Walker Oct. 7, 1975 [5 CARBAMOYL SULFOXIDE DERIVATIVES 57 BSTR CT [75] Inventor: Francis Harry Walker, Mill Valley. Intermediate compounds useful for manufacturing Calif. herbicidal active sulfoxide compounds are described [73] Assigneez staufler Chemical p y, herein. The compounds have the following generic formula:

Westport, Conn.

[22] Filed: Aug. 24, 1973 [2l] Appl. No.: 391,386 0 Related us. Application Data H [63] Continuation of Ser. No. 280,383, Aug. l4, 1972.

abandoned.

[52] U.S. Cl; 260/294.8 E; 71/94 whemin R is Select! from pyridylalkyly RI and R2 can [51] C070 213/52 be the same or different and can be selected from the [58] Field of Search 260/2946 Primary Examiner-Harry l, Moatz Attorney, Agent, or FirmDaniel C. Block group consisting of lower alkyl, cycloalkyl, alkenyl and benzyl.

2 Claims, No Drawings CARBAMOYL SULFOXIDE DERIVATIVES This is a continuation, of application Ser. No. 280,383, filed Aug. l4, I972, now abandoned.

DESCRIPTION OF THE INVENTION This invention is directed to a novel group of compounds which may be generally described as sulfoxide derivatives of thiocarbamates which are highly active herbicides. These compounds are represented by the generic formula:

wherein R, R, and R have been defined above. The reaction is carried out in the presence of a solvent such as chloroform, methylene chloride, benzene or toluene, and at a reduced temperature of from about 25C. to about C. The amount of oxidizing agent used must be at least one molar equivalent to form the sulfoxide derivative.

EXAMPLE I 9 g n/CZHS CHz'S" A solution was formed containing 6.0 g. (0.024 mole) S-(3-pyridylmethyl)-N-ethyl-N-butylthiocarbamate dissolved in 100 cc. of methylene chloride. This solution was cooled to l5C. in a dry ice bath. Then, 4.5 g. (0.026 mole) of m-chloroperoxybenzoic acid was added portionwise over a period of 1.5 minutes. The mixture was stirred for 1 hour and the temperature was raised to 5C. and held for 0.5 hours. Then, the mixture was warmed to room temperature. The reaction mixture was transferred to a separatory funnel and treated 4 times with ml. of a 5% sodium carbonate solution followed by 2 50 ml. water washes. After drying over MgSO,, the solvent was removed by vacuum to yield 5.0 g. of product, n 1.5471.

Other compounds were prepared in an analogous manner starting with the appropriate starting materials as outlined above. The following is a table of compounds representative of those embodied by the present invention. Compound numbers have been assigned to them and are used for identification throughout the balance of the specification.

TABLE l-Continued H ll RI R S-CN Compound Number R R, R

7 n-C,H, n-C,H

H ERBlClDAL SCREENING TESTS As previously mentioned, the novel compounds herein described are phytotoxic compounds which are useful and valuable in controlling various plants species. Compounds of this invention are tested as herbicides in the following manner.

A. Preemergence Herbicide Screening Test: Using an analytical balance, mg of the compound to be tested is weighed out on a piece of glassine weighing paper. The paper and compound are placed in a ml widemouth bottle and 3 ml of acetone containing 1% Tween 20 is added to dissolve the compound. 1f the material is not soluble in acetone, another solvent such as water, alcohol or dimethylformamide (DMF) is used instead. When DMF is used, only 0.5 ml or less is used to dissolve the compound and then another solvent is used to make the volume up to 3 ml. The 3 ml of solution is sprayed uniformly on the soil contained in a small Styrofoam flat one day after planting weed seeds in the flat of soil. A No. 152 DeVilbiss atomizer is used to apply the spray using compressed air at a pressure of 5 1b/sq.in. The rate of application is 8 lb/acre and the spray volume is 143 gal/acre.

On the day preceding treatment, the Styrofoam flat which is 7 inches long, 5 inches wide and 2.75 inches deep is filled to a depth of 2 inches with loamy sand soil. Seeds of seven different weed species are planted in individual rows using one species per row across the width of the flat. The seeds are covered with soil so that they are planted at a depth of 0.5 inch. The seeds used are hairy crabgrass (Digimria sanguinalis), yellow foxtail (Semria glauca), watergrass (Echinochloa crusgalli), red oat (Avena sativa), redroot pigweed (Amaranrhus retroflexus), Indian mustard (Brassica juncea) and curly dock (Rumex crispus). Ample seeds are planted to give about 20 to 50 seedlings per row after emergence depending on the size of the plants.

After treatment, the flats are placed in the greenhouse at a temperature of 70 to 85F and watered by sprinkling. Two weeks after treatment the degree of injury or control is determined by comparison with untreated chcck plants of the same age. The injury rating from O to 100% is recorded for each species as percent control with 0% representing no injury and 100% representing complete kill.

B. Postemergence Herbicide Screening Test: Seeds of six plant species, including hairy crabgrass, watergrass, red oat, mustard, curly dock and Pinto beans (Phaseolus vulgaris) are planted in the Styrofoan flats as described above for preemergence screening. The flats are placed in the greenhouse at to 85F and watered daily with a sprinkler. About 10 to 14 days after planting when the primary leaves of the bean plants are almost fully expanded and the first trifoliate leaves are just starting to form, the plants are sprayed. The spray is prepared by weighing out 20 mg of the test compound, dissolving it in 5 ml of acetone containing 1% Tween 20 and then adding 5 ml of water. The solution is sprayed on the foliage using a No. 152 DeVilbiss atomizer at an air pressure of 5 lb/sq.in. The spray concentration is 0.2% and the rate is 8 lb/acre. The spray volume is 476 gal/acre.

injury ratings are recorded 14 days after treatment. The rating system is the same as described above for the preemergence test.

The results of these tests are shown in Table 11.

TABLE II HERBICIDAL ACTIVITY SCREENING RESULTS Compound Percent Control at 8 lb/A Number Preemergenee Postemergence l 63 27 2 39 22 3 20 3 4 92 5 27 4O 6 49 2O 7 30 10 B 7 15 Average for seven species in the preemergence test and for six species in the postemergence test.

The compounds of the present invention can be used in any convenient form. Thus, the compounds can be made into emulsiflable liquids, emulsifiable concentrates, liquid, wettable powder, powders, granular or any other convenient form, and applied to the soil to control the undesired vegetation.

wherein R is pyridylmethyl, R and R can be the same or different and are selected from the group consisting of lower alkyl cyclohexyl, allyl and benzyl, comprising the steps of a. combining an oxidizing agent selected from the group consisting of peracetic acid and mchloroperoxybenzoic acid and a thiocarbamatc compound in a solvent system; said thiocarbamate having the following formula:

wherein R, R and R have been defined above;

b. maintaining the temperature between "25C. and

c. said oxidizing agent being present in an amount of at least one molar equivalent. 2. The process of claim 1 wherein the oxidizing agent is and m-chloroperoxybenzoic acid.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION PATENT NO. 3,910,935 DATED October 7, 1975 lNVENTORtSI 1 Francis Harry Walker It is certIfied that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below;

Column 3 Table I, the entry for Compound No. 8 under the heading 'R" should read and the entry under the heading "R ,should read Signed and Scaled this Eighth Day of March 1977 [SEAL] Amsr:

RUTH C. MASON C. MARSHALL DANN Arresting Officer (ummr'ssr'oner ufParenrs and Trademark: 

1. A PROCESS OF MANUFACTURING A PESICIDAL ACTIVE COMPOUND HAVING THE FOLLOWING FORMULA:
 2. The process of claim 1 wherein the oxidizing agent is and m-chloroperoxybenzoic acid. 